EP1928921A1 - Method for seed bed treatment before a polymerization reaction - Google Patents
Method for seed bed treatment before a polymerization reactionInfo
- Publication number
- EP1928921A1 EP1928921A1 EP06802002A EP06802002A EP1928921A1 EP 1928921 A1 EP1928921 A1 EP 1928921A1 EP 06802002 A EP06802002 A EP 06802002A EP 06802002 A EP06802002 A EP 06802002A EP 1928921 A1 EP1928921 A1 EP 1928921A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- reactor
- continuity additive
- polymerization reaction
- reaction
- flow improver
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 118
- 238000000034 method Methods 0.000 title claims abstract description 92
- 239000000654 additive Substances 0.000 claims abstract description 62
- 230000000996 additive effect Effects 0.000 claims abstract description 54
- 238000011068 loading method Methods 0.000 claims abstract description 33
- 239000002002 slurry Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 239000000843 powder Substances 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 72
- 239000002184 metal Substances 0.000 claims description 72
- 238000006243 chemical reaction Methods 0.000 claims description 56
- 150000007942 carboxylates Chemical class 0.000 claims description 48
- 150000003839 salts Chemical class 0.000 claims description 45
- -1 aluminum carboxylate Chemical class 0.000 claims description 39
- 125000004432 carbon atom Chemical group C* 0.000 claims description 31
- 239000002216 antistatic agent Substances 0.000 claims description 19
- 150000001336 alkenes Chemical class 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical group [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 claims description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 229940063655 aluminum stearate Drugs 0.000 claims description 10
- 239000008119 colloidal silica Substances 0.000 claims description 9
- 239000004711 α-olefin Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 125000005842 heteroatom Chemical group 0.000 claims description 7
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 238000010926 purge Methods 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052768 actinide Inorganic materials 0.000 claims description 4
- 150000001255 actinides Chemical class 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 4
- 150000002602 lanthanoids Chemical class 0.000 claims description 4
- 239000011236 particulate material Substances 0.000 claims description 4
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 4
- 125000005189 alkyl hydroxy group Chemical group 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- 150000002367 halogens Chemical class 0.000 claims 2
- 150000002763 monocarboxylic acids Chemical class 0.000 claims 2
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims 2
- 150000003627 tricarboxylic acid derivatives Chemical class 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 2
- 239000003054 catalyst Substances 0.000 description 55
- 239000007789 gas Substances 0.000 description 27
- 239000000203 mixture Substances 0.000 description 27
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 20
- 239000005977 Ethylene Substances 0.000 description 20
- 229920000642 polymer Polymers 0.000 description 17
- 230000008569 process Effects 0.000 description 17
- 239000000178 monomer Substances 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical class CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 6
- 239000003085 diluting agent Substances 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000002685 polymerization catalyst Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical class [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 230000000737 periodic effect Effects 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical class [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000010981 drying operation Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000012685 gas phase polymerization Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- CXKOGOLCUOXBQC-UHFFFAOYSA-K [B+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O Chemical class [B+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CXKOGOLCUOXBQC-UHFFFAOYSA-K 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 150000001343 alkyl silanes Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 125000005018 aryl alkenyl group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 229910021482 group 13 metal Inorganic materials 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 125000001905 inorganic group Chemical group 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-M margarate Chemical compound CCCCCCCCCCCCCCCCC([O-])=O KEMQGTRYUADPNZ-UHFFFAOYSA-M 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229940105132 myristate Drugs 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-M nonanoate Chemical compound CCCCCCCCC([O-])=O FBUKVWPVBMHYJY-UHFFFAOYSA-M 0.000 description 2
- JFOJYGMDZRCSPA-UHFFFAOYSA-J octadecanoate;tin(4+) Chemical class [Sn+4].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O JFOJYGMDZRCSPA-UHFFFAOYSA-J 0.000 description 2
- OXOUKWPKTBSXJH-UHFFFAOYSA-J octadecanoate;titanium(4+) Chemical class [Ti+4].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O OXOUKWPKTBSXJH-UHFFFAOYSA-J 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-M octanoate Chemical compound CCCCCCCC([O-])=O WWZKQHOCKIZLMA-UHFFFAOYSA-M 0.000 description 2
- 125000005474 octanoate group Chemical group 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-M oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC([O-])=O ZQPPMHVWECSIRJ-KTKRTIGZSA-M 0.000 description 2
- 229940049964 oleate Drugs 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- IUGYQRQAERSCNH-UHFFFAOYSA-M pivalate Chemical compound CC(C)(C)C([O-])=O IUGYQRQAERSCNH-UHFFFAOYSA-M 0.000 description 2
- 229950010765 pivalate Drugs 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000036316 preload Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- FRKHZXHEZFADLA-UHFFFAOYSA-L strontium;octadecanoate Chemical class [Sr+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O FRKHZXHEZFADLA-UHFFFAOYSA-L 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 description 2
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- 229940070710 valerate Drugs 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- GDDAJHJRAKOILH-QFXXITGJSA-N (2e,5e)-octa-2,5-diene Chemical compound CC\C=C\C\C=C\C GDDAJHJRAKOILH-QFXXITGJSA-N 0.000 description 1
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-N 0.000 description 1
- QTYUSOHYEPOHLV-FNORWQNLSA-N 1,3-Octadiene Chemical compound CCCC\C=C\C=C QTYUSOHYEPOHLV-FNORWQNLSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- BBDKZWKEPDTENS-UHFFFAOYSA-N 4-Vinylcyclohexene Chemical compound C=CC1CCC=CC1 BBDKZWKEPDTENS-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- 239000004915 4-vinylcyclohex-1-ene Substances 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VZHUBBUZNIULNM-UHFFFAOYSA-N Cyclohexyl butanoate Chemical class CCCC(=O)OC1CCCCC1 VZHUBBUZNIULNM-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Chemical class 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- WXCZUWHSJWOTRV-UHFFFAOYSA-N but-1-ene;ethene Chemical compound C=C.CCC=C WXCZUWHSJWOTRV-UHFFFAOYSA-N 0.000 description 1
- ULZZTKYVKFTVBQ-UHFFFAOYSA-N buta-1,2,3-triene;ethene Chemical compound C=C.C=C=C=C ULZZTKYVKFTVBQ-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012809 cooling fluid Substances 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- UGMCXQCYOVCMTB-UHFFFAOYSA-K dihydroxy(stearato)aluminium Chemical compound CCCCCCCCCCCCCCCCCC(=O)O[Al](O)O UGMCXQCYOVCMTB-UHFFFAOYSA-K 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- HKEBYUNPANBGPL-UHFFFAOYSA-N nona-2,4-diene Chemical compound CCCCC=CC=CC HKEBYUNPANBGPL-UHFFFAOYSA-N 0.000 description 1
- MAMCJGWPGQJKLS-UHFFFAOYSA-N nona-2,7-diene Chemical compound CC=CCCCC=CC MAMCJGWPGQJKLS-UHFFFAOYSA-N 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 150000002848 norbornenes Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920000570 polyether Chemical class 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- HEPBQSXQJMTVFI-UHFFFAOYSA-N zinc;butane Chemical compound [Zn+2].CCC[CH2-].CCC[CH2-] HEPBQSXQJMTVFI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/002—Scale prevention in a polymerisation reactor or its auxiliary parts
- C08F2/005—Scale prevention in a polymerisation reactor or its auxiliary parts by addition of a scale inhibitor to the polymerisation medium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/34—Polymerisation in gaseous state
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- the invention pertains to methods for seed bed treatment before performance of a polymerization reaction (e.g., an olefin polymerization reaction) to improve continuity of the reaction.
- a polymerization reaction e.g., an olefin polymerization reaction
- One commonly used method for producing polymers is gas phase polymerization.
- a conventional gas phase fluidized bed reactor contains a fluidized dense-phase bed including a mixture of reaction gas, polymer (resin) particles, catalyst, and catalyst modifiers.
- a "seed bed” is typically loaded into the reactor or is present in the reactor from a previous polymerization operation.
- the seed bed is (or consists essentially of) granular material that is or includes polymer material.
- the polymer material can but need not be identical to the desired end product of the reaction.
- An example of seed bed material is metallocene polyethylene.
- a continuity additive (“CA") into a reactor during a fluidized bed polymerization reaction to reduce sheeting and/or fouling in the reactor during polymerization.
- CA continuity additive
- a continuity additive is typically not catalytic, but is typically combined with a catalyst (and typically also with a flow improver) before or after being introduced into the reactor.
- CAs are aluminum stearate, other metal stearates, and Atmer AS 990 (an ethoxylated stearyl amine, available from Ciba Specialty Chemicals Co, Basel, Switzerland).
- U.S. Patent 6,300,436 and U.S. 6,306,984 describe an olefin polymerization process (e.g., a gas phase or slurry phase process) in a reactor the presence of a catalyst composition comprising a carboxylate metal salt.
- the carboxylate metal salt is a continuity additive ("CA") which significantly reduces sheeting and/or fouling in the reactor during polymerization.
- CA continuity additive
- the catalyst composition is produced by combining, contacting, blending and/or mixing a catalyst system (e.g., a supported catalyst system) with the carboxylate metal salt.
- the catalyst system can be a transition metal catalyst compound (e.g., a bulky ligand metallocene-type catalyst compound).
- the carboxylate metal salt can be blended (e.g., tumble dry blended) with a supported catalyst system or polymerization catalyst comprising a carrier.
- the polymerization catalyst can be dry and free flowing and the metal carboxylate salt mixed or blended with the catalyst can be in solid form.
- the carboxylate metal salt is added to a reactor (containing reactants and a catalyst system) during polymerization without previously having been combined, blended, contacted, or mixed with the catalyst system.
- Examples include saturated, unsaturated, aliphatic, aromatic or saturated cyclic carboxylic acid salts where the carboxylate ligand has preferably from 2 to 24 carbon atoms, such as acetate, propionate, butyrate, valerate, pivalate, caproate, isobuytlacetate, t-butyl-acetate, caprylate, heptanate, pelargonate, undecanoate, oleate, octoate, palmitate, myristate, margarate, stearate, arachate and tercosanoate.
- the carboxylate ligand has preferably from 2 to 24 carbon atoms, such as acetate, propionate, butyrate, valerate, pivalate, caproate, isobuytlacetate, t-butyl-acetate, caprylate, heptanate, pelargonate, undecanoate, oleate, octoate, palmitate, myristate, mar
- the metal portion includes a metal from the Periodic Table of Elements selected from the group of Al, Mg, Ca, Sr, Sn, Ti, V, Ba, Zn, Cd, Hg, Mn, Fe 5 . Co, Ni, Pd, Li and Na.
- Examples of carboxylate metal salts that may be suitable for use as continuity additives are represented by the general formula M(Q) x (OOCR) y , where M is a metal from Groups 1 to 16 and the Lanthanide and Actinide series, preferably from Groups 1 to 7 and 13 to 16 (preferably Groups 2 and 13, and most preferably Group 13); Q is a halogen or hydrogen, or a hydroxy, hydroxide, alkyl, alkoxy, aryloxy, siloxy, silane sulfonate group, or siloxane; R is a hydrocarbyl radical having from 2 to 100 carbon atoms, preferably 4 to 50 carbon atoms; and x is an integer from 0 to 3 and y is an integer from 1 to 4 and the sum of x and y is equal to the valence of the metal.
- y is an integer from 1 to 3, preferably 1 to 2, especially where M is a Group-13 metal.
- R in the above formula include hydrocarbyl radicals having 2 to 100 carbon atoms that include alkyl, aryl, aromatic, aliphatic, cyclic, saturated or unsaturated hydrocarbyl radicals.
- R can be a hydrocarbyl radical having greater than or equal to 8 carbon atoms (preferably greater than or equal to 17 carbon atoms) or R can be a hydrocarbyl radical having from 17 to 90 carbon atoms (preferably from 17 to 54 carbon atoms).
- Non-limiting examples of Q in the above formula include one or more, same or different, hydrocarbon containing group such as alkyl; cycloalkyl, aryl, alkenyl, arylalkyl, arylalkenyl or alkylaryl, alkylsilane, arylsilane, alkylamine, arylamine, alkyl phosphide,; alkoxy having from 1 to 30 carbon atoms.
- the hydrocarbon containing group may be linear, branched, or even substituted.
- Q can be an inorganic group such as a halide, sulfate or phosphate.
- a carboxylate metal salt employed as a CA has a melting point from about 3O 0 C to about 250°C (preferably from about 100 0 C to about 200 0 C).
- the carboxylate metal salt employed as a CA is an aluminum stearate having a melting point in the range of from about 135°C to about 65 0 C.
- the carboxylate metal salt employed as a CA has a melting point greater than the polymerization temperature in the reactor.
- carboxylate metal salts that may be suitable for use as continuity additives include titanium stearates, tin stearates, calcium stearates, zinc stearates, boron stearates and strontium stearates.
- a carboxylate metal salt is combined (for use as a continuity additive) with an antistatic agent such as a fatty amine, for example, Atmer AS 990/2 zinc additive, a blend of ethoxylated stearyl amine and zinc stearate, or Atmer AS 990/3, a blend of ethoxylated stearyl amine, zinc stearate and octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate. Both the AS 990/2 and 990/3 blends are available from Crompton Corporation of Memphis, Tennessee.
- U.S. Patents 6,482,903 and 6,660,815 teach performance of an olefin polymerization process (e.g., a gas phase or slurry phase process) in a reactor in the presence of a catalyst composition including a catalyst system (e.g., a supported bulky ligand metallocene-type catalyst system), at least one carboxylate metal salt, and at least one flow improver.
- the flow improver can be a colloidal particulate material (e.g., Snowtex colloidal silica, available from Nissan Chemical Industries, Tokyo, Japan, or another colloidal silica).
- colloidal particulate material e.g., Snowtex colloidal silica, available from Nissan Chemical Industries, Tokyo, Japan, or another colloidal silica.
- Patent 6,482,903 include a colloidal silica (e.g., Cabosil, available from Cabot), a fumed silica, a syloid, and alumina.
- U.S. Patents 6,482,903 and 6,660,815 teach that the carboxylate metal salt is preferably contacted with the flow improver prior to use in the reactor or contact with a polymerization catalyst, and that a catalyst system can be combined, contacted, blended, or mixed with a composition of at least one carboxylate metal salt and at least one flow improver before use in a reactor.
- U.S. Patents 6,482,903 and 6,660,815 also teach that because carboxylate metal salts are difficult to handle (e.g., because their morphology is poor and because they have low bulk density and fluffy consistency), a combination of a carboxylate metal salt and a flow improver can be handled and combined with a supported catalyst system in a substantially improved manner than can the carboxylate metal salt alone.
- U.S. Patents 6,300,436 and 6,306,984 teach that when starting up a polymerization reaction, especially a gas phase process, there is a higher tendency for operability problems to occur. They also teach performing the initial stages of such a reaction (before the process has stabilized) in the presence of a polymerization catalyst and carboxylate metal salt mixture to reduce or eliminate start-up problems. They also teach implementing a transition after the initial stages of the reaction (i.e., when the reactor has begun to operate in a stable state) to cause the reaction to proceed in the presence of the same (or a different) polymerization catalyst but not in the presence of the carboxylate metal salt.
- the present inventors have recognized that a reactor can be vulnerable to sheeting and/or fouling during the critical initial stage(s) of a polymerization reaction (before the reaction has stabilized) even if each such initial stage is performed in the presence of a CA, if the concentration of the CA is low.
- the present inventors have also recognized that the concentration of CA in a reactor is typically too low to eliminate this vulnerability if the CA is introduced during the initial stage(s) of the polymerization reaction (i.e., after the reaction has begun).
- a continuity additive (“CA") is pre-loaded into a reactor (in which a seed bed is present and a polymerization reaction can be performed) or a mixture of a CA and a seed bed are pre-loaded into a reactor (in which a polymerization reaction can be performed).
- a polymerization reaction is then performed in the reactor.
- a flow improver and a CA are pre-loaded into a reactor in which a seed bed is present, or a mixture of a CA, a flow improver, and a seed bed are pre-loaded into a reactor (in which a polymerization reaction can be performed).
- a polymerization reaction is then performed in the reactor.
- a CA is pre-loaded into a seed bed present in a reactor from a previous polymerization operation.
- a polymerization reaction is then performed in the reactor.
- a CA with a flow aid is pre-loaded into a seed bed present in a reactor from a previous polymerization operation.
- a polymerization reaction is then performed in the reactor.
- Pre-loading of the reactor in accordance with the invention can significantly improve continuity of the polymerization reaction during at least one initial stage (before the reaction has stabilized), including by reducing sheeting and fouling.
- the initial stage (or stages) of a polymerization reaction are the most critical in the sense that there is typically a higher tendency for operability problems to occur before the reaction has stabilized than after it has stabilized.
- the expression that a reactor (in which a polymerization reaction can be performed) is "pre-loaded" with a CA (or a combination of a CA and at least one other substance) denotes that the CA (or combination) is loaded into the reactor before the start of the polymerization reaction.
- a seed bed in a reactor is always "pre-loaded” in the reactor in the sense that it is loaded prior to and in preparation for a reaction which may or may not subsequently occur (in contrast with being loaded at or after the start of the reaction).
- Preloading in accordance with the invention is typically accomplished by loading a seed bed (typically consisting essentially of granular material) into a reactor before the start of a polymerization reaction, and then combining a CA (or a combination of a CA and at least one other substance) with the seed bed in the reactor before the start of the reaction.
- pre-loading in accordance with the invention can be accomplished by preparing treated seed bed material (by combining seed bed material with at least one CA) and then loading the treated seed bed material into the reactor before the start of a polymerization reaction, or loading a CA (or a combination of a CA and at least one other substance) into a reactor (in which a seed bed is already present) before the start of a polymerization reaction.
- the invention is a method comprising the steps of:
- Steps (a) and (b) can be, and typically are, performed with air and moisture present in the reactor. Typically, moisture and air are removed from the reactor (e.g., by performing a drying operation) after steps (a) and (b) but before step (c) to prepare the reactor for performance of the reaction.
- pre-loading the reactor (in step (b)) with the CA or combination eliminates or significantly reduces sheeting and fouling that would otherwise occur (if the reactor were not pre-loaded with the CA or combination) during at least one initial stage of the polymerization reaction, and optionally also otherwise improves continuity during at least one initial stage of the polymerization reaction.
- pre-loading of at least one CA in accordance with the invention can be accomplished by treating a seed bed existing in a reactor (from a previous polymerization operation) before the start of a new polymerization reaction.
- the seed bed can be from a polymerization reaction that used the same or a different catalyst system as the catalyst system to be employed in the new polymerization reaction.
- the invention is a method comprising the steps of:
- step (b) after step (a), performing a polymerization reaction in the reactor.
- air and moisture are present (with the seed bed) in the reactor during step (a).
- the moisture and air are removed from the reactor (e.g., by performing a drying or purging operation) after step (a) but before step (b) to prepare the reactor for performance of the reaction.
- a CA is pre-loaded in dry form (e.g., as a powder) into the reactor.
- the CA is pre-loaded into the reactor in liquid or slurry form (e.g., as an oil slurry) or as a component of a mixture of solids, liquids, or at least one solid and at least one liquid.
- a solid and/or a liquid CA can be pre-loaded (in accordance with some embodiments) with a carrier liquid (e.g., a hydrocarbon or hydrocarbon oil) into a reactor.
- the dry CA can be combined with a flow improver and the combination of CA and flow improver then loaded into the reactor.
- a CA and a flow improver can be sequentially loaded into the reactor, and then mixed together (and mixed with a seed bed) in the reactor after both the CA and flow improver have been separately loaded into the reactor.
- the improved flow properties of the combined CA and flow improver allow for delivery of the CA as a solid (e.g., to pre-load the reactor with a specific, predetermined amount of CA for smooth start up operation).
- a specific amount of CA is pre-loaded into a reactor based on the weight of a seed bed in (or to be loaded into) the reactor.
- embodiments of the invention can include any of the steps of: preloading a CA into a reactor and then loading a seed bed into the reactor; loading a seed bed into a reactor and then pre-loading a CA into the reactor; simultaneously pre-loading a CA and a seed bed into a reactor; and combining (e.g., mixing) a seed bed with a CA and then loading the combination into a reactor.
- the CA maybe loaded (e.g., pre-loaded) with a flow aid.
- a CA is pre-loaded into a reactor in any of a number of different ways, including by: pretreatment of a seedbed in the reactor with a flow-aid modified CA; introduction of the CA with (and during) loading of a seed bed into the reactor (for example, the seed bed material can be combined with the CA before the combination is loaded into the reactor); introduction of the CA during the reactor condition build-up stage after purging is complete; introduction of the CA directly into the seed bed via a tube inserted into the seed bed (e.g., through a catalyst support tube); introduction of dry CA (that has been pre- weighed) into the reactor; and introduction of dry CA (that has been pre-weighed into a metal container) into the reactor using pressurized nitrogen.
- catalyst support tube denotes a tube (typically a heavy walled tube) extending from about 0.1 R R to 0.6 RR into a reactor through which another tube optionally be placed, where R R is the radius of the reactor.
- CA may be pre-loaded in accordance with the invention either through a catalyst support tube or another tube optionally placed through the inner opening of a catalyst support tube.
- FIG. 1 is a simplified cross-sectional view of a system including fluidized bed reactor (10), which can be pre-loaded in accordance with the invention.
- FIG. 2 is a simplified cross-sectional view of another fluidized bed reactor which can be pre-loaded in accordance with the invention.
- FIG. 3 is a simplified cross-sectional view of another fluidized bed reactor which can be pre-loaded in accordance with the invention.
- Fig. 4 is a formula identifying a class of antistatic agents that can be employed as continuity additives in accordance with some embodiments of the invention.
- Fig. 5 is a formula identifying a class of antistatic agents that can be employed as continuity additives in accordance with some embodiments of the invention.
- FIG. 1 A system including a reactor that can be pre-loaded in accordance with the invention will be described with reference to Figure 1.
- the Fig. 1 system includes fluidized bed reactor 10.
- Reactor 10 has a bottom end 11, a top section 19, a cylindrical (straight) section 14 between bottom end 11 and top section 19, and a distributor plate 12 within section 14.
- the diameter of each horizontal cross-section of section 19 is greater than the diameter of straight section 14.
- dense-phase surface 18 is the boundary between lean phase material present within reactor 10 (above dense-phase surface 18) and dense-phase material 16 within reactor 10 (in the volume bounded by section 14, plate 12, and surface 18).
- freeboard surface 20 of reactor 10 includes the inner surface of top section 19 and the portion of the inner surface of section 14 above surface 18.
- the Fig. 1 system also has a cooling control loop which includes circulating gas cooler 30 and compressor 32, coupled with reactor 10 as shown.
- a cooling control loop which includes circulating gas cooler 30 and compressor 32, coupled with reactor 10 as shown.
- the cooled circulating gas flows from cooler 30 through inlet 34 into reactor 10, then propagates upward through the bed and out from reactor 10 via outlet 33.
- the cooling fluid (whose temperature has increased during its flow through reactor 10) is pumped by compressor 32 from outlet 33 back to cooler 30.
- Temperature sensors near the inlet and outlet of cooler 30 typically provide feedback to cooler 30 and/or compressor 32 to control the amount by which cooler 30 reduces the temperature of the fluid entering its inlet and/or flow rate through compressor 32.
- a seed bed is pre-loaded in reactor 10 before the start of a polymerization reaction therein.
- the seed bed typically consists essentially of granular material.
- dense-phase material 16 in the reactor includes the seed bed.
- a continuity additive ("CA") and a seed bed are pre-loaded into a reactor (e.g., reactor 10) in which a polymerization reaction can be performed.
- a polymerization reaction is then performed in the reactor.
- a flow improver, a CA, and a seed bed are pre-loaded into a reactor (e.g., reactor 10) in which a polymerization reaction can be performed.
- a polymerization reaction is then performed in the reactor.
- Pre-loading of reactor 10 with a CA (or a CA and a flow improver) and a seed bed in accordance with the invention can significantly improve continuity of a polymerization reaction subsequently performed in the reactor during the reaction's initial stage or stages (before the reaction has stabilized), including by reducing sheeting and fouling.
- pre-loading in accordance with the invention is accomplished by loading the seed bed into reactor 10 and then combining a CA (or a combination of a CA and a flow improver) with the seed bed in the reactor before the start of a polymerization reaction in the reactor.
- the invention is a method comprising the steps of:
- Steps (c) after steps (a) and (b), performing a polymerization reaction in the reactor can be performed either simultaneously or sequentially.
- Steps (a) and (b) can be and typically are performed with air and moisture present in the reactor.
- moisture and air are removed from the reactor (e.g., by performing a drying operation) after steps (a) and (b) but before step (c) to prepare the reactor for performance of the reaction.
- moisture and air are removed from the reactor by performing a drying operation.
- Pre-loading of reactor 10 with a CA (or a CA and a flow improver) in accordance with the invention when a seed bed exists in the reactor, can significantly improve continuity of a polymerization reaction subsequently performed in the reactor during the reaction's initial stage or stages (before the reaction has stabilized), including by reducing sheeting and fouling.
- pre-loading in accordance with the invention is accomplished by having an existing seed bed in reactor 10 and then combining a CA (or a combination of a CA and a flow improver) with the seed bed in the reactor before the start of a polymerization reaction in the reactor.
- the invention is a method comprising the steps of:
- step (b) after step (a), performing a polymerization reaction in the reactor.
- air and moisture are present (with the seed bed) in the reactor during step (a).
- the moisture and air are removed from the reactor (e.g., by performing a drying or purging operation) after step (a) but before step (b) to prepare the reactor for performance of the reaction.
- the invention is a method comprising the steps of:
- step (b) after step (a), performing a polymerization reaction in the reactor.
- air and moisture are present (with the seed bed) in the reactor during step (a).
- the moisture and air are removed from the reactor (e.g., by performing a drying or purging operation) after step (a) but before step (b) to prepare the reactor for performance of the reaction.
- the CA is loaded into reactor 10 in dry form (e.g., as a powder).
- the CA is loaded into reactor 10 in liquid or slurry form (e.g., as an oil slurry) or in a mixture of solids, liquids, or at least one solid and at least one liquid.
- the CA typically comprises 2%-50% by weight of the slurry (or 5%- 35% by weight of the slurry in preferred embodiments, or 10%-30% by weight of the slurry in more preferred embodiments).
- the dry CA can be combined with a flow improver and the combination of CA and flow improver then loaded into the reactor.
- the CA and flow improver can be sequentially loaded into the reactor, and then mixed together (and mixed with a seed bed) in the reactor after both the CA and flow improver have been separately loaded into the reactor.
- the improved flow properties of the combined CA and flow improver allow for delivery of the CA as a solid (e.g., to pre-load the reactor with a specific, predetermined amount of CA for smooth start up operation).
- a specific amount of CA is pre-loaded into reactor 10 based on the weight of a seed bed in (or to be loaded into) the reactor.
- a CA is pre-loaded into reactor 10 (or another reactor) in any of a number of different ways, including by: pretreatment of a seed bed in the reactor with a flow-aid modified CA (a CA combined with a flow improver); introduction of the CA with (and during) loading of a seed bed into the reactor; introduction of the CA during the reactor condition build-up stage after purging is complete; introduction of the CA directly into the seed bed via a tube located within the seedbed (For example, CA 7 can be pre-loaded into a seed bed in reactor 10 of Fig.
- catalyst support tubes 8 typically, a total of eight support tubes 8 would extend through the wall of reactor 10, with the outlet end of each within the seed bed. However, only four of tubes 8 are shown in Fig. 1); and introduction of dry CA (that has been pre- weighed into a metal container) into the reactor using pressurized nitrogen.
- the CA pre-loaded into a reactor in accordance with the invention can have any composition provided that it will improve continuity of a polymerization reaction subsequently performed in the reactor during at least one initial stage of the reaction (before the reaction has stabilized), including by reducing sheeting and fouling.
- Examples of CAs suitable for improving continuity of a variety of polymerization reactions are described in above-referenced U.S. Patents 6,482,903; 6,660,815; 6,306,984; and 6,300,436.
- a CA is not catalytic but is combined with a catalyst (and optionally also with a flow improver) before or after being introduced into the reactor.
- CAs examples include: aluminum stearate, other metal stearates, Atmer AS 990 (an ethoxylated stearyl amine, available from Ciba Specialty Chemicals Co, Basel, Switzerland), and carboxylate metal salts.
- Carboxylate metal salts that may be suitable for use in accordance with the invention as continuity additives (CAs) include any mono- or di- or tricarboxylic acid salt with a metal portion from the Periodic Table of Elements. Examples include saturated, unsaturated, aliphatic, aromatic or saturated cyclic carboxylic acid salts where the carboxylate ligand has preferably from 2 to 24 carbon atoms, such as acetate, propionate, butyrate, valerate, pivalate, caproate, isobuytlacetate, t-butyl-acetate, caprylate, heptanate, pelargonate, undecanoate, oleate, octoate, palmitate, myristate, margarate, stearate, arachate and tercosanoate.
- CAs continuity additives
- Examples of the metal portion includes a metal from the Periodic Table of Elements selected from the group of Al, Mg, Ca, Sr, Sn, Ti, V, Ba, Zn, Cd, Hg, Mn, Fe, Co, Ni, Pd, Li and Na.
- Carboxylate metal salts that may be suitable for use in accordance with the invention as CAs include those represented by the general formula M(Q) x (OOCR) y , where M is a metal from Groups 1 to 16 and the Lanthanide and Actinide series, preferably from Groups 1 to 7 and 13 to 16 (preferably Groups 2 and 13, and most preferably Group 13); Q is a halogen, hydrogen, or a hydroxy, hydroxide, alkyl, alkoxy, aryloxy, siloxy, silane sulfonate group, or siloxane; R is a hydrocarbyl radical having from 2 to 100 carbon atoms, preferably 4 to 50 carbon atoms; and x is an integer from 0 to 3 and y is an integer from 1 to 4 and the sum of x and y is equal to the valence of the metal, hi a preferred embodiment of the above formula, y is an integer from 1 to 3, preferably 1 to 2, especially where M is a Group- 13 metal.
- M
- Non-limiting examples of R in the above formula include hydrocarbyl radicals having 2 to 100 carbon atoms that include alkyl, aryl, aromatic, aliphatic, cyclic, saturated or unsaturated hydrocarbyl radicals.
- R can be a hydrocarbyl radical having greater than or equal to 8 carbon atoms (preferably greater than or equal to 17 carbon atoms) or R can be a hydrocarbyl radical having from 17 to 90 carbon atoms (preferably from 17 to 54 carbon atoms).
- Non-limiting examples of Q in the above formula include one or more, same or different, hydrocarbon containing group such as alkyl; cycloalkyl, aryl, alkenyl, arylalkyl, arylalkenyl or alkylaryl, alkylsilane, arylsilane, alkylamine, arylamine, alkyl phosphide,; alkoxy having from 1 to 30 carbon atoms.
- the hydrocarbon containing group may be linear, branched, or even substituted.
- Q can be an inorganic group such as a halide, sulfate or phosphate.
- a carboxylate metal salt that may be suitable for use as a CA in accordance with the invention is an aluminum carboxylate.
- it can be one of the aluminum mono, di- and tri-stearates, aluminum octoates, oleates and cyclohexylbutyrates.
- the carboxylate metal salt can be (CH 3 (CH 2 ) I6 COO) 3 Al, an aluminum tri-stearate (preferred melting point 115°C), (CH 3 (CH 2 ) 16 COO) 2 —A— OH, an aluminum di-stearate (preferred melting point 145 0 C), or CH 3 (CH 2 ) ⁇ COO — Al — (OH) 2 , an aluminum mono- stearate (preferred melting point 155°C).
- carboxylate metal salts include Crompton Aluminum Stearate #18, Crompton Aluminum Stearate #22, Crompton Aluminum Stearate #132 and Crompton Aluminum Stearate EA Food Grade, all available from Crompton Corporation, of Memphis, Tennessee.
- a carboxylate metal salt employed as a CA in accordance with the invention has a melting point from about 3O 0 C to about 25O 0 C (preferably from about 100 0 C to about 200 0 C).
- the carboxylate metal salt employed as a CA in accordance with the invention is an aluminum stearate having a melting point in the range of from about 135°C to about 65°C.
- the carboxylate metal salt employed as a CA has a melting point greater than the polymerization temperature in the reactor.
- carboxylate metal salts that may be suitable for use as continuity additives in accordance with the invention include titanium stearates, tin stearates, calcium stearates, zinc stearates, boron stearate and strontium stearates.
- a carboxylate metal salt is combined (for use as a continuity additive to be pre-loaded into a reactor) with an antistatic agent such as a fatty amine, for example, Atmer AS 990/2 zinc additive, a blend of ethoxylated stearyl amine and zinc stearate, or Atmer AS 990/3, a blend of ethoxylated stearyl amine, zinc stearate and octadecyl-3,5-di-tert-butyl-4- hydroxyhydrocinnamate. Both the AS 990/2 and 990/3 blends are available from Crompton Corporation of Memphis, Tennessee.
- An example of a flow improver that can be combined with a CA (e.g., a carboxylate metal salt) in dry form and then pre-loaded in a reactor in accordance with a class of embodiments of the invention for improving continuity of a subsequent olefin polymerization process in the presence of a catalyst composition including a catalyst system (e.g., a supported bulky ligand metallocene-type catalyst system), is a colloidal particulate material (e.g., Snowtex colloidal silica, available from Nissan Chemical Industries, Tokyo, Japan, or Aerosil colloidal silica, available from Degussa, or another colloidal silica).
- a catalyst system e.g., a supported bulky ligand metallocene-type catalyst system
- a colloidal particulate material e.g., Snowtex colloidal silica, available from Nissan Chemical Industries, Tokyo, Japan, or Aerosil colloidal silica, available from Degussa, or another colloidal silica
- a flow improver for use in accordance with the invention are a colloidal silica (e.g., Cabosil, available from Cabot), a fumed silica, a syloid, and alumina.
- a substance that can be employed as a CA is an antistatic agent of any of the types described in U.S. Patent 6,245,868, issued June 12, 2001.
- an antistatic agent is any organic compound containing at least one electron rich heteroatom from Groups IV, V and/or VI and a hydrocarbyl moiety.
- typical heteroatoms include silicon, oxygen, nitrogen, phosphorus, and sulfur.
- the antistatic agent should also contain at least one active hydrogen atom attached to the heteroatom.
- the hydrocarbyl moiety it is preferable that the hydrocarbyl moiety have a molecular weight sufficient to give it solubility in typical hydrocarbon solvents, such as, for example a cyclic aliphatic or aromatic hydrocarbon, for example toluene.
- Examples of antistatic agents that can be employed as CAs in accordance with some embodiments of the invention are represented by the formula, R TO XR' ⁇ , where R is a branched or straight chain hydrocarbyl group or substituted hydrocarbyl group or groups having one or more carbon atoms, R' is an alkyl hydroxy group such as — CH 2 CH 2 OH, X is at least one heteroatom (an O, N, P or S atom or a combination thereof), and n is such that the formula has no net charge.
- Non limiting examples are the following general structures with R being a hydrocarbyl group are: RNH 2 , R 2 NH, (R 1 C(OH) n R")NH 2 , (R 1 C(OH) n IT) 2 NH, 1 RCONH 2 , RCONHR, RN(ROH) 2 , RCO 2 H, RC(O)NROH, RC(S)OH, and R 2 PO 2 H.
- These compounds include amines, alcohols, phenols, thiols, silanols, diols, polyols, glycols, acids, and ethers.
- antistatic agents that can be employed as CAs in accordance with some embodiments of the invention are expressed by the formula shown in Fig. 4, where R 3 is hydrogen or a branched or preferably a straight chain alkyl group having 1 to 50 carbon atoms. R 1 and R 2 can be the same or different and can be the same as R 3 or contain another heteroatom (e.g., O, N, P or S).
- R 3 is hydrogen or a branched or preferably a straight chain alkyl group having 1 to 50 carbon atoms.
- R 1 and R 2 can be the same or different and can be the same as R 3 or contain another heteroatom (e.g., O, N, P or S).
- Other examples of antistatic agents that can be employed as CAs in accordance with some embodiments of the invention are expressed by the formula shown in Fig.
- R 1 is hydrogen or a linear or branched alkyl group of from 1 to 50 carbon atoms (preferably greater than 12 carbon atoms)
- R 2 can be a hydroxy group such a (CH 2 ) ⁇ OH radical, where x is an integer from 1 to 50 (preferably from 2 to 25).
- antistatic agents that can be employed as CAs in accordance with some embodiments of the invention are quaternary ammonium compounds, and hydrocarbyl sulfates or phosphates.
- Tertiary amines, ethoxylated amines and polyether compounds are other examples of antistatic agents that can be employed as CAs in accordance with some embodiments of the invention.
- Antistatic agents employed as CAs in accordance with the invention can be synthetically derived or otherwise.
- one or more sensors can be used to monitor the presence of the CA in the reactor's cycle gas loop. In response to the output of such a sensor, the operator can determine whether more CA should be loaded into the reactor.
- a CA is pre-loaded into a reactor to cause the CA to be present in the reactor in a concentration (relative to the weight of a seed bed also present in the reactor) in one of the following ranges: 2 ppm by weight to 3% by weight, or preferably 5 ppm to 1000 ppm, or more preferably 5 ppm to 200 ppm, or more preferably 10 ppm to 100 ppm, or most preferably 15 ppm to 50 ppm by weight.
- Reactor 10 can be implemented as a mLLDPE (metallocene-catalyzed, linear low-density polyethylene) reactor.
- mLLDPE metalocene-catalyzed, linear low-density polyethylene
- Fig. 2 is a simplified cross-sectional view of another fluidized bed reactor which can be pre-loaded in accordance with the invention.
- the Fig. 2 reactor has a cylindrical (straight) section between its bottom end and its top section, and a distributor plate 12 within the straight section.
- dense- phase surface 88 is the boundary between lean phase material present within the reactor (above dense-phase surface 88) and dense-phase material 86 within the reactor (in the volume bounded by the straight section, plate 12, and surface 88).
- Fig. 3 is a simplified cross-sectional view of another fluidized bed reactor which can be pre-loaded in accordance in accordance with the invention.
- the Fig. 1 is a simplified cross-sectional view of another fluidized bed reactor which can be pre-loaded in accordance in accordance with the invention.
- dense-phase surface 98 is the boundary between lean phase material present within the reactor (above dense-phase surface 98) and dense-phase material 96 within the reactor (in the volume bounded by the straight section, plate 12, and surface 98).
- a continuous gas phase fluidized bed reactor is pre-loaded in accordance with the invention before it operates to perform polymerization as follows.
- the fluidized bed is made up of polymer granules.
- Liquid or gaseous feed streams of the primary monomer and hydrogen together with liquid or gaseous comonomer are combined and introduced into the recycle gas line upstream of the fluidized bed.
- the primary monomer is ethylene and the comonomer is hexene.
- the individual flow rates of ethylene, hydrogen and comonomer are controlled to maintain fixed composition targets.
- the ethylene concentration is controlled to maintain a constant ethylene partial pressure.
- the hydrogen is controlled to maintain a constant hydrogen to ethylene mole ratio.
- the hexene is controlled to maintain a constant hexene to ethylene mole ratio.
- concentration of all gases is measured by an on-line gas chromatograph to ensure relatively constant composition in the recycle gas stream.
- a solid or liquid catalyst is injected directly into the fluidized bed using purified nitrogen as a carrier. Its rate is adjusted to maintain a constant production rate.
- the reacting bed of growing polymer particles is maintained in a fluidized state by the continuous flow of the make up feed and recycle gas through the reaction zone. In some implementations, a superficial gas velocity of 1-3 ft/sec is used to achieve this, and the reactor is operated at a total pressure of 300 psig.
- the temperature of the recycle gas is continuously adjusted up or down to accommodate any changes in the rate of heat generation due to the polymerization.
- the fluidized bed is maintained at a constant height by withdrawing a portion of the bed at a rate equal to the rate of formation of particulate product.
- the product is removed semi-continuously via a series of valves into a fixed volume chamber, which is simultaneously vented back to the reactor. This allows for highly efficient removal of the product, while at the same time recycling a large portion of the unreacted gases back to the reactor.
- This product is purged to remove entrained hydrocarbons and treated with a small steam of humidified nitrogen to deactivate any trace quantities of residual catalyst.
- a reactor is pre-loaded in accordance with the invention and then operated to perform polymerization using any of a variety of different processes (e.g., solution, slurry, or gas phase processes).
- the reactor can be a fluidized bed reactor that is operated to produce polyolefin polymers by a gas phase polymerization process.
- This type of reactor and means for operating such a reactor are well known.
- the polymerization medium can be mechanically agitated or fluidized by the continuous flow of the gaseous monomer and diluent.
- a polymerization reaction is performed in a reactor that has been pre-loaded in accordance with the invention.
- the reaction can be a continuous gas phase process (e.g., a fluid bed process).
- a fluidized bed reactor for performing such a process typically comprises a reaction zone and a so-called velocity reduction zone.
- the reaction zone comprises a bed of growing polymer particles, formed polymer particles and a minor amount of catalyst particles fluidized by the continuous flow of the gaseous monomer and diluent to remove heat of polymerization through the reaction zone.
- some of the re-circulated gases may be cooled and compressed to form liquids that increase the heat removal capacity of the circulating gas stream when readmitted to the reaction zone.
- This method of operation is referred to as "condensed mode.”
- a suitable rate of gas flow may be readily determined by simple experiment. Make up of gaseous monomer to the circulating gas stream is at a rate equal to the rate at which particulate polymer product and monomer associated therewith is withdrawn from the reactor and the composition of the gas passing through the reactor is adjusted to maintain an essentially steady state gaseous composition within the reaction zone.
- the gas leaving the reaction zone is passed to the velocity reduction zone where entrained particles are removed.
- the gas is compressed in a compressor, passed through a heat exchanger wherein the heat of polymerization is removed, and then returned to the reaction zone.
- the reactor temperature of the fluid bed process can range from 30°C or 40°C or 50°C to 90°C or 100°C or 110 0 C or 120 0 C or 150°C.
- the reactor temperature is operated at the highest temperature that is feasible taking into account the sintering temperature of the polymer product within the reactor.
- the polymerization temperature or reaction temperature typically must be below the melting or "sintering" temperature of the polymer to be formed.
- the upper temperature limit in one embodiment is the melting temperature of the polyolefin produced in the reactor.
- a reactor that has been pre-loaded in accordance with the invention is then operated to effect polymerization by a slurry polymerization process.
- a slurry polymerization process generally uses pressures in the range of from 1 to 50 atmospheres and even greater and temperatures in the range of 0°C to 120°C, and more particularly from 30°C to 100 0 C.
- a suspension of solid, particulate polymer is formed in a liquid polymerization diluent medium to which monomer and comonomers and often hydrogen along with catalyst are added.
- the suspension including diluent is intermittently or continuously removed from the reactor where the volatile components are separated from the polymer and recycled, optionally after a distillation, to the reactor.
- the liquid diluent employed in the polymerization medium is typically an alkane having from 3 to 7 carbon atoms, a branched alkane in one embodiment.
- the medium employed should be liquid under the conditions of polymerization and relatively inert. When a propane medium is used the process must be operated above the reaction diluent critical temperature and pressure. In one embodiment, a hexane, isopentane or isobutane medium is employed.
- a reactor that has been pre-loaded in accordance with the invention is operated to perform particle form polymerization, or a slurry process in which the temperature is kept below the temperature at which the polymer goes into solution.
- a reactor that has been preloaded in accordance with the invention is a loop reactor or one of a plurality of stirred reactors in series, parallel, or combinations thereof.
- slurry processes include continuous loop or stirred tank processes.
- a reactor that has been pre-loaded in accordance with some embodiments of the invention can be operated to produce homopolymers of olefins, e.g., ethylene, and/or copolymers, terpolymers, and the like, of olefins, particularly ethylene, and at least one other olefin.
- olefins e.g., ethylene, and/or copolymers, terpolymers, and the like.
- the olefins may contain from 2 to 16 carbon atoms in one embodiment; and in another embodiment, ethylene and a comonomer comprising from 3 to 12 carbon atoms in another embodiment; and ethylene and a comonomer comprising from 4 to 10 carbon atoms in yet another embodiment; and ethylene and a comonomer comprising from 4 to 8 carbon atoms in yet another embodiment.
- a reactor that has been pre-loaded in accordance with the invention can produce polyethylenes.
- Such polyethylenes can be homopolymers of ethylene and interpolymers of ethylene and at least one ⁇ -olefin wherein the ethylene content is at least about 50% by weight of the total monomers involved.
- Exemplary olefins that may be utilized in embodiments of the invention are ethylene, propylene, 1-butene, 1- pentene, 1-hexene, 1-he ⁇ tene, 1-octene, 4-methylpent-l-ene, 1-decene, 1- dodecene, 1-hexadecene and the like.
- polyenes such as 1,3-hexadiene, 1,4-hexadiene, cyclopentadiene, dicyclopentadiene, 4- vinylcyclohex-1-ene, 1,5-cyclooctadiene, 5-vinylidene-2-norbomene and 5-vinyl- 2-norbomene, and olefins formed in situ in the polymerization medium.
- polyenes such as 1,3-hexadiene, 1,4-hexadiene, cyclopentadiene, dicyclopentadiene, 4- vinylcyclohex-1-ene, 1,5-cyclooctadiene, 5-vinylidene-2-norbomene and 5-vinyl- 2-norbomene, and olefins formed in situ in the polymerization medium.
- olefins are formed in situ in the polymerization medium, the formation of polyolefins containing long chain branching may occur.
- comonomers may be present in the polymerization reactor.
- the comonomer may be present at any level with the ethylene or propylene monomer that will achieve the desired weight percent incorporation of the comonomer into the finished resin, hi one embodiment of polyethylene production, the comonomer is present with ethylene in a mole ratio range of from 0.0001 (comonomer: ethylene) to 50, and from 0.0001 to 5 in another embodiment, and from 0.0005 to 1.0 in yet another embodiment, and from 0.001 to 0.5 in yet another embodiment.
- the amount of ethylene present in the polymerization reactor may range to up to 1000 atmospheres pressure in one embodiment, and up to 500 atmospheres pressure in another embodiment, and up to 200 atmospheres pressure in yet another embodiment, and up to 100 atmospheres in yet another embodiment, up to 50 atmospheres in yet another embodiment, and up to 30 atmospheres in yet another embodiment.
- Hydrogen gas is often used in olefin polymerization to control the final properties of the polyolefin.
- increasing concentrations (partial pressures) of hydrogen increase the melt flow (MF) and/or melt index (MI) of the polyolefin generated.
- the MF or MI can thus be influenced by the hydrogen concentration.
- the amount of hydrogen in the polymerization can be expressed as a mole ratio relative to the total polymerizable monomer, for example, ethylene, or a blend of ethylene and hexane or propene.
- the amount of hydrogen used in some polymerization processes is an amount necessary to achieve the desired MF or MI of the final polyolefin resin.
- the mole ratio of hydrogen to total monomer (H 2 monomer) is greater than 0.00001.
- the mole ratio is greater than 0.0005 in another embodiment, greater than 0.001 in yet another embodiment, less than 10 in yet another embodiment, less than 5 in yet another embodiment, less than 3 in yet another embodiment, and less than 0.10 in yet another embodiment, wherein a desirable range may comprise any combination of any upper mole ratio limit with any lower mole ratio limit described herein.
- the amount of hydrogen in the reactor at any time may range to up to 10 ppm in one embodiment, or up to 100 or 3000 or 4000 or 5000 ppm in other embodiments, or between 10 ppm and 5000 ppm in yet another embodiment, or between 500 ppm and 2000 ppm in another embodiment.
- a reactor that is pre-loadable in accordance with some embodiments of the invention is an element of a staged reactor employing two or more reactors in series, wherein one reactor may produce, for example, a high molecular weight component and another reactor may produce a low molecular weight component.
- a reactor that has been pre-loaded in accordance with some embodiments of the invention can be operated to implement a slurry or gas phase process in the presence of a bulky ligand metallocene-type catalyst system and in the absence of, or essentially free of, any scavengers, such as triethylaluminum, trimethylaluminum, tri-isobutylaluminum and tri-n-hexylaluminum and diethyl aluminum chloride, dibutyl zinc and the like.
- any scavengers such as triethylaluminum, trimethylaluminum, tri-isobutylaluminum and tri-n-hexylaluminum and diethyl aluminum chloride, dibutyl zinc and the like.
- essentially free it is meant that these compounds are not deliberately added to the reactor or any reactor components.
- a reactor that has been pre-loaded in accordance with some embodiments of the invention can be operated to perform a reaction that employs one or more catalysts combined with up to 10 wt% of a metal-fatty acid compound, such as, for example, an aluminum stearate, based upon the weight of the catalyst system (or its components).
- a metal-fatty acid compound such as, for example, an aluminum stearate
- Other metals that may be suitable include other Group 2 and Group 5-13 metals.
- a solution of the metal-fatty acid compound is fed into the reactor.
- the metal-fatty acid compound is mixed with the catalyst and fed into the reactor separately. These agents may be mixed with the catalyst or may be fed into the reactor in a solution or a slurry with or without the catalyst system or its components.
- supported catalyst(s) can be combined with activators and can be combined by tumbling and/or other suitable means, with up to 2.5 wt% (by weight of the catalyst composition) of an antistatic agent, such as an ethoxylated or methoxylated amine, an example of which is Atmer AS-990 (Ciba Specialty Chemicals, Basel, Switzerland).
- an antistatic agent such as an ethoxylated or methoxylated amine, an example of which is Atmer AS-990 (Ciba Specialty Chemicals, Basel, Switzerland).
- antistatic compositions include the Octastat family of compounds, more specifically Octastat 2000, 3000, and 5000.
- Metal fatty acids and antistatic agents can be added as either solid slurries or solutions as separate feeds into the reactor.
- One advantage of this method of addition is that it permits on-line adjustment of the level of the additive.
- Examples of polymers that can be produced in accordance with the invention include the following: homopolymers and copolymers of C2-C18 alpha olefins; polyvinyl chlorides, ethylene propylene rubbers (EPRs); ethylene- propylene diene rubbers (EPDMs); polyisoprene; polystyrene; polybutadiene; polymers of butadiene copolymerized with styrene; polymers of butadiene copolymerized with isoprene; polymers of butadiene with acrylonitrile; polymers of isobutylene copolymerized with isoprene; ethylene butene rubbers and ethylene butene diene rubbers; and polychloroprene
- Monomers that can be present in a reactor that has been pre-loaded in accordance with the invention include one or more of: C2-C18 alpha olefins such as ethylene, propylene, and optionally at least one diene, for example, hexadiene, dicyclopentadiene, octadiene including methyloctadiene (e.g., 1 -methyl- 1,6- octadiene and 7-methyl-l,6-octadiene), norbornadiene, and ethylidene norbornene; and readily condensable monomers, for example, isoprene, styrene, butadiene, isobutylene, chloroprene, acrylonitrile, cyclic olefins such as norbornenes.
- C2-C18 alpha olefins such as ethylene, propylene, and optionally at least one diene, for example, hexadiene
- Fluidized bed polymerization (e.g., mechanically stirred and/or gas fiuidized) reactions can be performed in some reactors that have been pre-loaded in accordance with the invention.
- Such a reaction can be any type of fluidized polymerization reaction and can be carried out in a single reactor or multiple reactors such as two or more reactors in series.
- any of many different types of polymerization catalysts can be used in a polymerization process performed in a reactor that has been pre-loaded in accordance with the invention.
- a single catalyst may be used, or a mixture of catalysts may be employed, if desired.
- the catalyst can be soluble or insoluble, supported or unsupported. It may be a prepolymer, spray dried with or without a filler, a liquid, or a solution, slurry/suspension or dispersion. These catalysts are used with cocatalysts and promoters well known in the art.
- alkylaluminums typically these are alkylaluminums, alkylaluminum halides, alkylaluminum hydrides, as well as aluminoxanes.
- suitable catalysts include Ziegler-Natta catalysts, Chromium based catalysts, Vanadium based catalysts (e.g., vanadium oxychloride and vanadium acetylacetonate), Metallocene catalysts and other single-site or single-site-like catalysts, Cationic forms of metal halides (e.g., aluminum trihalides), anionic initiators (e.g., butyl lithiums), Cobalt catalysts and mixtures thereof, Nickel catalysts and mixtures thereof, rare earth metal catalysts (i.e., those containing a metal having an atomic number in the Periodic Table of 57 to 103), such as compounds of cerium, lanthanum, praseodymium, gadolinium and neodymium.
- a polymerization reaction performed in a reactor that has been pre-loaded in accordance with the invention can employ other additives, such as (for example) inert particulate particles.
- additives such as (for example) inert particulate particles.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Pretreatment Of Seeds And Plants (AREA)
- Soy Sauces And Products Related Thereto (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/236,998 US20070073012A1 (en) | 2005-09-28 | 2005-09-28 | Method for seed bed treatment before a polymerization reaction |
PCT/US2006/032621 WO2007037839A1 (en) | 2005-09-28 | 2006-08-22 | Method for seed bed treatment before a polymerization reaction |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1928921A1 true EP1928921A1 (en) | 2008-06-11 |
EP1928921B1 EP1928921B1 (en) | 2010-02-17 |
Family
ID=37441633
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP06802002A Active EP1928921B1 (en) | 2005-09-28 | 2006-08-22 | Method for seed bed treatment before a polymerization reaction |
Country Status (11)
Country | Link |
---|---|
US (2) | US20070073012A1 (en) |
EP (1) | EP1928921B1 (en) |
JP (1) | JP5069242B2 (en) |
KR (1) | KR20080068029A (en) |
CN (2) | CN105367691A (en) |
AT (1) | ATE458011T1 (en) |
BR (1) | BRPI0616461B1 (en) |
CA (1) | CA2622258A1 (en) |
DE (1) | DE602006012338D1 (en) |
RU (1) | RU2424251C2 (en) |
WO (1) | WO2007037839A1 (en) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070073012A1 (en) * | 2005-09-28 | 2007-03-29 | Pannell Richard B | Method for seed bed treatment before a polymerization reaction |
JP5055761B2 (en) * | 2005-12-19 | 2012-10-24 | 住友化学株式会社 | Process for producing olefin polymer |
EP2227495B1 (en) * | 2007-12-31 | 2013-01-23 | Dow Global Technologies LLC | Process for polymerizing olefin-based polymers |
WO2009157770A1 (en) * | 2008-06-26 | 2009-12-30 | Basf Catalysts Llc | Process for the production of an alpha-olefin polymer |
WO2010071798A1 (en) | 2008-12-18 | 2010-06-24 | Univation Technologies, Llc | Method for seed bed treatment for a polymerization reaction |
US8637615B2 (en) | 2009-12-18 | 2014-01-28 | Univation Technologies, Llc | Methods for making polyolefin products having different shear thinning properties and haze |
US9221935B2 (en) | 2011-06-09 | 2015-12-29 | Nova Chemicals (International) S.A. | Modified phosphinimine catalysts for olefin polymerization |
US11186654B2 (en) * | 2016-12-20 | 2021-11-30 | Exxonmobil Chemical Patents Inc. | Methods for controlling start up conditions in polymerization processes |
KR20190058032A (en) | 2017-11-21 | 2019-05-29 | 롯데케미칼 주식회사 | Method for producing olefin polymers by using metallocene catalysts |
WO2019173030A1 (en) | 2018-03-08 | 2019-09-12 | Exxonmobil Chemical Patents Inc. | Methods of preparing and monitoring a seed bed for polymerization reactor startup |
EP4330294A1 (en) | 2021-04-30 | 2024-03-06 | ExxonMobil Chemical Patents Inc. | Processes for transitioning between different polymerization catalysts in a polymerization reactor |
Family Cites Families (127)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5066737A (en) * | 1990-10-22 | 1991-11-19 | Shell Oil Company | Olefin polymerization catalyst |
US3221002A (en) * | 1963-09-26 | 1965-11-30 | Cabot Corp | Process for polymerization utilizing a surface treated inorganic solid catalyst |
US3487112A (en) * | 1967-04-27 | 1969-12-30 | Monsanto Co | Vapor phase hydroformylation process |
US3687920A (en) * | 1971-01-25 | 1972-08-29 | Union Carbide Corp | Polymerization of olefins with silane modified catalyst system |
US4115639A (en) * | 1971-06-24 | 1978-09-19 | Union Carbide Corporation | Ethylene polymerization with ether modified catalyst |
US4086409A (en) * | 1973-12-20 | 1978-04-25 | Union Carbide Corporation | Ethylene polymerization with siloxane modified catalyst |
GB1443074A (en) * | 1974-01-14 | 1976-07-21 | Ici Ltd | Olefin polymerisation process |
IT1037112B (en) * | 1975-03-28 | 1979-11-10 | Montedison Spa | CATALYSTS FOR THE POLYMERIZATION OF OLFINES |
US4077904A (en) * | 1976-06-29 | 1978-03-07 | Union Carbide Corporation | Olefin polymerization process and catalyst therefor |
US4101445A (en) * | 1976-09-22 | 1978-07-18 | Union Carbide Corporation | Preparation of modified and activated chromocene catalysts for ethylene polymerization |
DE2731067C3 (en) * | 1977-07-09 | 1981-11-26 | Bunawerke Hüls GmbH, 4370 Marl | Process for the preparation of polybutadiene with a high content of monomer units in a cis-1,4 structure |
EP0004417B2 (en) * | 1978-03-23 | 1990-02-28 | Imperial Chemical Industries Plc | Gas-phase olefin polymerisation system and process for operating it |
US4302565A (en) * | 1978-03-31 | 1981-11-24 | Union Carbide Corporation | Impregnated polymerization catalyst, process for preparing, and use for ethylene copolymerization |
US4302566A (en) * | 1978-03-31 | 1981-11-24 | Union Carbide Corporation | Preparation of ethylene copolymers in fluid bed reactor |
US4482687A (en) * | 1979-10-26 | 1984-11-13 | Union Carbide Corporation | Preparation of low-density ethylene copolymers in fluid bed reactor |
US4376062A (en) * | 1979-11-28 | 1983-03-08 | Union Carbide Corporation | Spheroidal polymerization catalyst, process for preparing, and use for ethylene polymerization |
US4379758A (en) * | 1980-12-24 | 1983-04-12 | Union Carbide Corporation | Catalyst composition for polymerizing ethylene |
US5019633A (en) * | 1980-12-24 | 1991-05-28 | Technology Corporation | Catalyst composition for polymerizing ethylene |
US4532311A (en) * | 1981-03-26 | 1985-07-30 | Union Carbide Corporation | Process for reducing sheeting during polymerization of alpha-olefins |
CA1174800A (en) | 1981-08-24 | 1984-09-18 | Charles Cozewith | Gas phase method for producing copolymers of ethylene and higher alpha-olefins |
US4376191A (en) * | 1981-10-01 | 1983-03-08 | Union Carbide Corporation | Use of dialkylzinc compounds to initiate polymerization of ethylene with chromium oxide catalysts |
CA1219994A (en) * | 1981-12-24 | 1987-03-31 | Nobunori Maehara | Process for producing polybutadiene rubber with enhanced mechanical strength |
DE3366573D1 (en) * | 1982-06-24 | 1986-11-06 | Bp Chimie Sa | Process for the polymerization and copolymerization of alpha-olefins in a fluidized bed |
US4560671A (en) * | 1983-07-01 | 1985-12-24 | Union Carbide Corporation | Olefin polymerization catalysts adapted for gas phase processes |
FR2555182B1 (en) * | 1983-11-23 | 1986-11-07 | Bp Chimie Sa | PROCESS FOR THE PREPARATION OF A SUPPORTED CATALYST FOR THE COPOLYMERIZATION OF ETHYLENE WITH SUPERIOR ALPHA-OLEFINS |
DE3600611A1 (en) * | 1986-01-11 | 1987-07-16 | Basf Ag | USE OF ANTISTATICS TO PREVENT COATING IN THE PRODUCTION OF ULTRA HIGH MOLECULAR POLYETHYLENE IN GAS PHASE REACTORS |
DE3600610A1 (en) * | 1986-01-11 | 1987-07-16 | Basf Ag | USE OF ANTISTATICS TO PREVENT COATING IN THE PRODUCTION OF ETHYLENE POLYMERISATS IN GAS PHASE REACTORS |
US4755495A (en) * | 1986-02-27 | 1988-07-05 | Union Carbide Corporation | Process for activation of titanium and vanadium catalysts useful in ethylene polymerization |
US4810397A (en) * | 1986-03-26 | 1989-03-07 | Union Oil Company Of California | Antifoulant additives for high temperature hydrocarbon processing |
US4689437A (en) * | 1986-07-21 | 1987-08-25 | Union Carbide Corporation | Oligomerization to alpha-olefins |
US4719193A (en) * | 1986-09-30 | 1988-01-12 | Union Carbide Corporation | Processes for preparing polyethylene catalysts by heating catalyst precursors |
US4855370A (en) * | 1986-10-01 | 1989-08-08 | Union Carbide Corporation | Method for reducing sheeting during polymerization of alpha-olefins |
FR2609036B1 (en) * | 1986-12-29 | 1989-04-14 | Bp Chimie Sa | POLYMERIZATION OR COPOLYMERIZATION OF ETHYLENE IN THE GASEOUS PHASE IN THE PRESENCE OF A PREPOLYMER COMPRISING A CHROMIUM OXIDE CATALYST |
US5264405A (en) * | 1989-09-13 | 1993-11-23 | Exxon Chemical Patents Inc. | Monocyclopentadienyl titanium metal compounds for ethylene-α-olefin-copolymer production catalysts |
US5055438A (en) * | 1989-09-13 | 1991-10-08 | Exxon Chemical Patents, Inc. | Olefin polymerization catalysts |
US5198401A (en) * | 1987-01-30 | 1993-03-30 | Exxon Chemical Patents Inc. | Ionic metallocene catalyst compositions |
US5026795A (en) * | 1987-02-24 | 1991-06-25 | Phillips Petroleum Co | Process for preventing fouling in a gas phase polymerization reactor |
EP0282929B2 (en) * | 1987-03-14 | 1997-10-22 | Mitsubishi Kasei Corporation | Method for producing a propylene-alpha-olefin block copolymer |
US5093415A (en) * | 1987-05-19 | 1992-03-03 | Union Carbide Chemicals & Plastics Technology Corporation | Process for producing stereoregular polymers having a narrow molecular weight distribution |
FR2628110B1 (en) * | 1988-03-03 | 1994-03-25 | Bp Chimie | CATALYST FOR POLYMERIZATION OF ZIEGLER-NATTA-TYPE OLEFINS, SUPPORTED ON SPHERICAL MAGNESIUM CHLORIDE PARTICLES, AND PROCESS FOR PREPARING THE SAME |
FR2646426B2 (en) * | 1988-09-13 | 1991-08-16 | Bp Chemicals Sa | PROCESS AND APPARATUS FOR POLYMERIZATION OF ALPHA-OLEFIN IN THE GASEOUS PHASE IN THE PRESENCE OF AN ACTIVITY-SLOWING AGENT |
DE3833445A1 (en) * | 1988-10-01 | 1990-04-05 | Basf Ag | PREVENTION OF COLORED IMPURITIES IN THE PRODUCTION OF ULTRA HIGH-MOLECULAR ETHYLENE POLYMERISATES BY MEANS OF A TITANIUM-CONTAINING CATALYST SYSTEM |
DE3833444A1 (en) * | 1988-10-01 | 1990-04-05 | Basf Ag | PREVENTION OF COLORED IMPURITIES IN THE PRODUCTION OF ULTRA HIGH-MOLECULAR ETHYLENE POLYMERISATES BY MEANS OF A TITANIUM-CONTAINING CATALYST SYSTEM |
US5376612A (en) * | 1989-08-10 | 1994-12-27 | Phillips Petroleum Company | Chromium catalysts and process for making chromium catalysts |
NZ235032A (en) | 1989-08-31 | 1993-04-28 | Dow Chemical Co | Constrained geometry complexes of titanium, zirconium or hafnium comprising a substituted cyclopentadiene ligand; use as olefin polymerisation catalyst component |
US5227440A (en) * | 1989-09-13 | 1993-07-13 | Exxon Chemical Patents Inc. | Mono-Cp heteroatom containing Group IVB transition metal complexes with MAO: supported catalysts for olefin polymerization |
US5057475A (en) * | 1989-09-13 | 1991-10-15 | Exxon Chemical Patents Inc. | Mono-Cp heteroatom containing group IVB transition metal complexes with MAO: supported catalyst for olefin polymerization |
US5064802A (en) * | 1989-09-14 | 1991-11-12 | The Dow Chemical Company | Metal complex compounds |
FR2660926B1 (en) * | 1990-04-11 | 1992-07-31 | Bp Chemicals Snc | ALPHA-OLEFIN PREPOLYMER CONTAINING A TRANSITIONAL METAL AND PROCESS FOR THE POLYMERIZATION OF ALPHA-OLEFIN IN THE GAS PHASE USING THE PREPOLYMER. |
PL166690B1 (en) * | 1990-06-04 | 1995-06-30 | Exxon Chemical Patents Inc | Method of obtaining polymers of olefins |
US5070055A (en) * | 1990-06-29 | 1991-12-03 | Union Carbide Chemicals And Plastics Technology Corporation | Novel coimpregnated vanadium-zirconium catalyst for making polyethylene with broad or bimodal MW distribution |
JP2545006B2 (en) * | 1990-07-03 | 1996-10-16 | ザ ダウ ケミカル カンパニー | Addition polymerization catalyst |
US5239022A (en) * | 1990-11-12 | 1993-08-24 | Hoechst Aktiengesellschaft | Process for the preparation of a syndiotactic polyolefin |
DE59104869D1 (en) * | 1990-11-12 | 1995-04-13 | Hoechst Ag | 2-Substituted bisindenyl metallocenes, process for their preparation and their use as catalysts in olefin polymerization. |
DE59107926D1 (en) * | 1990-11-12 | 1996-07-18 | Hoechst Ag | Metallocenes with ligands from 2-substituted indenyl derivatives, processes for their preparation and their use as catalysts |
US5243001A (en) * | 1990-11-12 | 1993-09-07 | Hoechst Aktiengesellschaft | Process for the preparation of a high molecular weight olefin polymer |
US5369196A (en) | 1990-11-30 | 1994-11-29 | Idemitsu Kosan Co., Ltd. | Production process of olefin based polymers |
DE4120009A1 (en) * | 1991-06-18 | 1992-12-24 | Basf Ag | SOLUBLE CATALYST SYSTEMS FOR THE PRODUCTION OF POLYALK-1-ENEN WITH HIGH MOLES |
US5126414A (en) * | 1991-10-11 | 1992-06-30 | Mobil Oil Corporation | Control of oligomer level in low pressure polyethylene reactor systems |
EP0537686B1 (en) * | 1991-10-15 | 2005-01-12 | Basell Polyolefine GmbH | Process for preparing an olefinpolymer by using metallocenes having specially substituted indenylligands |
US5233049A (en) * | 1991-10-29 | 1993-08-03 | Occidental Chemical Corporation | Highly fluorinated bis-imides |
US5331071A (en) * | 1991-11-12 | 1994-07-19 | Nippon Oil Co., Ltd. | Catalyst components for polymerization of olefins |
DE69222317T2 (en) * | 1991-11-25 | 1998-02-12 | Exxon Chemical Patents, Inc., Baytown, Tex. | POLYIONIC TRANSITION METAL CONTAINER COMPOSITION |
DE69224463T2 (en) * | 1991-11-28 | 1998-07-09 | Showa Denko Kk | Novel metallocene and process for making polyolefins using the same |
EP0549252A1 (en) | 1991-12-23 | 1993-06-30 | BP Chemicals Limited | Process for the gas-phase polymerisation of alpha-olefins in a fluidized-bed reactor |
BE1005888A3 (en) * | 1992-01-13 | 1994-03-01 | Solvay | Continuous process for removing residual monomers or an aqueous polymer latex synthetic and device for its implementation. |
IT1262933B (en) * | 1992-01-31 | 1996-07-22 | Montecatini Tecnologie Srl | PROCESS FOR THE ALFA-OLEFINE GAS POLYMERIZATION |
US5374696A (en) * | 1992-03-26 | 1994-12-20 | The Dow Chemical Company | Addition polymerization process using stabilized reduced metal catalysts |
EP0578838A1 (en) | 1992-04-29 | 1994-01-19 | Hoechst Aktiengesellschaft | Olefin polymerization catalyst, process for its preparation, and its use |
US5317036A (en) * | 1992-10-16 | 1994-05-31 | Union Carbide Chemicals & Plastics Technology Corporation | Gas phase polymerization reactions utilizing soluble unsupported catalysts |
US5332706A (en) * | 1992-12-28 | 1994-07-26 | Mobil Oil Corporation | Process and a catalyst for preventing reactor fouling |
US5539069A (en) | 1993-08-10 | 1996-07-23 | Mitsui Petrochemical Industries, Ltd. | Olefin polymerization catalysts and methods of olefin polymerization |
DE4334045A1 (en) * | 1993-10-06 | 1995-04-13 | Bayer Ag | Catalyst, its production and use for gas phase polymerization of conjugated dienes |
US5670438A (en) | 1993-10-27 | 1997-09-23 | Phillips Petroleum Company | Catalyst compositions and catalytic processes |
FI96867C (en) * | 1993-12-27 | 1996-09-10 | Borealis Polymers Oy | The fluidized bed reactor |
DE69419893T2 (en) * | 1993-12-27 | 1999-12-02 | Mitsui Chemicals, Inc. | Catalyst and process for olefin polymerization |
IT1274016B (en) * | 1994-02-21 | 1997-07-14 | Spherilene Srl | PROCESS FOR THE POLYMERIZATION IN THE GAS PHASE OF THE A-OLEFINS |
US5473020A (en) * | 1994-06-30 | 1995-12-05 | Phillips Petroleum Company | Polymer bound ligands, polymer bound metallocenes, catalyst systems, preparation, and use |
US5461123A (en) * | 1994-07-14 | 1995-10-24 | Union Carbide Chemicals & Plastics Technology Corporation | Gas phase fluidized bed polyolefin polymerization process using sound waves |
US5643847A (en) * | 1994-08-03 | 1997-07-01 | Exxon Chemical Patents Inc. | Supported ionic catalyst composition |
US5539124A (en) * | 1994-12-19 | 1996-07-23 | Occidental Chemical Corporation | Polymerization catalysts based on transition metal complexes with ligands containing pyrrolyl ring |
US5554775A (en) * | 1995-01-17 | 1996-09-10 | Occidental Chemical Corporation | Borabenzene based olefin polymerization catalysts |
US5880241A (en) * | 1995-01-24 | 1999-03-09 | E. I. Du Pont De Nemours And Company | Olefin polymers |
GB9502870D0 (en) | 1995-02-14 | 1995-04-05 | Zeneca Ltd | Chiral compounds |
US5527752A (en) * | 1995-03-29 | 1996-06-18 | Union Carbide Chemicals & Plastics Technology Corporation | Catalysts for the production of polyolefins |
US5637660A (en) * | 1995-04-17 | 1997-06-10 | Lyondell Petrochemical Company | Polymerization of α-olefins with transition metal catalysts based on bidentate ligands containing pyridine or quinoline moiety |
CA2176623C (en) | 1995-05-16 | 2000-07-25 | Purna Chand Sishta | Production of polyethylene using stereoisomeric metallocenes |
US5661095A (en) * | 1995-06-06 | 1997-08-26 | Quantum Chemical Corporation | Olefin polymerization catalyst component supported on a copolymer of an olefin and an unsaturated silane |
DE59600760D1 (en) | 1995-06-12 | 1998-12-10 | Targor Gmbh | Transition metal compound |
IT1275777B1 (en) * | 1995-07-06 | 1997-10-17 | Enichem Spa | METALLOCENIC CATALYST FOR THE (CO) POLYMERIZATION OF OLEFINS |
IT1277468B1 (en) | 1995-08-09 | 1997-11-10 | Enichem Spa | CATALYST FOR THE (CO) POLYMERIZATION OF OLEFINS AND PROCESS USING THE SAME |
EP0768322A1 (en) | 1995-10-16 | 1997-04-16 | Sumitomo Chemical Company, Limited | Method for preparing catalyst component for olefin polymerization, catalyst for olefin polymerization and process for producing olefin polymer with the catalyst |
US5869585A (en) * | 1995-10-30 | 1999-02-09 | Mobil Oil Corporation | Multi-component catalyst systems for olefin polymerization |
US5744417A (en) * | 1996-05-02 | 1998-04-28 | Lyondell Petrochemical Company | Supported catalyst |
CZ170897A3 (en) | 1996-06-06 | 1997-12-17 | Union Carbide Chem Plastic | Control of static charge in the course of polymerization process during which metallocene catalyst is used |
CN1178222A (en) | 1996-06-06 | 1998-04-08 | 联合碳化化学品及塑料技术公司 | Process for controlling static in polymerizations utilizing metallocene catalysts |
DE19624581C2 (en) | 1996-06-20 | 1999-02-04 | Targor Gmbh | Transition metal compound and a process for their preparation, and their use |
US5852146A (en) | 1996-06-27 | 1998-12-22 | Union Carbide Chemicals & Plastics Technology Corporation | Catalyst for the production of olefin polymers |
GB9613814D0 (en) | 1996-07-02 | 1996-09-04 | Bp Chem Int Ltd | Supported polymerisation catalysts |
CA2259582A1 (en) | 1996-07-23 | 1998-01-29 | Stephan James Mclain | Polymerization processes for olefins |
US5731392A (en) * | 1996-09-20 | 1998-03-24 | Mobil Oil Company | Static control with TEOS |
WO1998016311A1 (en) * | 1996-10-15 | 1998-04-23 | Northwestern University | Phenolate constrained geometry metallocene olefin polymerization catalyst, method of making, and method of using |
DE69705186T2 (en) | 1996-10-30 | 2002-03-14 | Repsol Quimica S.A., Madrid | Catalyst systems for the (co) polymerization of alpha olefins |
US6008662A (en) | 1996-10-31 | 1999-12-28 | Oxford Instruments America, Inc. | Apparatus and method for measuring conditions in fluidized beds |
US5849655A (en) | 1996-12-20 | 1998-12-15 | Fina Technology, Inc. | Polyolefin catalyst for polymerization of propylene and a method of making and using thereof |
KR19980060611A (en) * | 1996-12-31 | 1998-10-07 | 김영환 | Titanium Silicide Manufacturing Method |
US5854363A (en) | 1997-01-08 | 1998-12-29 | Phillips Petroleum Company | (Omega-alkenyl) (cyclopentacarbyl) metallocene compounds |
US5856547A (en) * | 1997-01-08 | 1999-01-05 | Phillips Petroleum Company | Organo omega-alkenyl cyclopentacarbyl silane compounds |
US5747406A (en) * | 1997-01-10 | 1998-05-05 | Union Carbide Chemicals & Plastics Technology Corporation | Catalyst composition for the production of olefin polymers |
US5851945A (en) | 1997-02-07 | 1998-12-22 | Exxon Chemical Patents Inc. | Olefin polymerization catalyst compositions comprising group 5 transition metal compounds stabilized in their highest metal oxidation state |
US5756611A (en) * | 1997-02-21 | 1998-05-26 | Lyondell Petrochemical Company | α-olefin polymerization catalysts |
SE518145C2 (en) * | 1997-04-18 | 2002-09-03 | Sandvik Ab | Multilayer coated cutting tool |
TWI246520B (en) | 1997-04-25 | 2006-01-01 | Mitsui Chemicals Inc | Processes for olefin polymerization |
US6245868B1 (en) * | 1998-05-29 | 2001-06-12 | Univation Technologies | Catalyst delivery method, a catalyst feeder and their use in a polymerization process |
US7354880B2 (en) * | 1998-07-10 | 2008-04-08 | Univation Technologies, Llc | Catalyst composition and methods for its preparation and use in a polymerization process |
DE19835467A1 (en) * | 1998-08-06 | 2000-02-17 | Elenac Gmbh | Solid reactor with antistatic coating for carrying out reactions in the gas phase |
US6111034A (en) * | 1998-12-31 | 2000-08-29 | Union Carbide Chemicals & Plastics Technology Corporation | Static control in olefin polymerization |
US6482903B1 (en) * | 1999-12-15 | 2002-11-19 | Univation Technologies, Llc | Method for preparing a supported catalyst system and its use in a polymerization process |
GB0027990D0 (en) * | 2000-11-16 | 2001-01-03 | Bp Chemicals Snc | Polymerisation process |
US6914027B2 (en) * | 2000-12-01 | 2005-07-05 | Univation Technologies, Llc | Polymerization reactor operability using static charge modifier agents |
US6608149B2 (en) | 2000-12-04 | 2003-08-19 | Univation Technologies, Llc | Polymerization process |
EP1308464A1 (en) * | 2001-10-19 | 2003-05-07 | BP Chemicals S.N.C. | Process for the gas-phase (co-)polymerisation of olefins in a fluidised bed reactor |
US6831140B2 (en) * | 2002-12-26 | 2004-12-14 | Univation Technologies, Llc | Static measurement and detection in a gas phase polyethylene reactor |
US20050148742A1 (en) * | 2004-01-02 | 2005-07-07 | Hagerty Robert O. | Method for controlling sheeting in gas phase reactors |
US7985811B2 (en) * | 2004-01-02 | 2011-07-26 | Univation Technologies, Llc | Method for controlling sheeting in gas phase reactors |
US20070073012A1 (en) * | 2005-09-28 | 2007-03-29 | Pannell Richard B | Method for seed bed treatment before a polymerization reaction |
TW200613326A (en) * | 2004-05-20 | 2006-05-01 | Exxonmobil Chemical Patents Inc | Polymerization process |
-
2005
- 2005-09-28 US US11/236,998 patent/US20070073012A1/en not_active Abandoned
-
2006
- 2006-08-22 CN CN201510882881.9A patent/CN105367691A/en active Pending
- 2006-08-22 DE DE602006012338T patent/DE602006012338D1/en active Active
- 2006-08-22 WO PCT/US2006/032621 patent/WO2007037839A1/en active Application Filing
- 2006-08-22 CN CNA2006800362167A patent/CN101277983A/en active Pending
- 2006-08-22 EP EP06802002A patent/EP1928921B1/en active Active
- 2006-08-22 CA CA002622258A patent/CA2622258A1/en not_active Abandoned
- 2006-08-22 BR BRPI0616461-7A patent/BRPI0616461B1/en active IP Right Grant
- 2006-08-22 KR KR1020087009925A patent/KR20080068029A/en not_active Application Discontinuation
- 2006-08-22 JP JP2008533354A patent/JP5069242B2/en active Active
- 2006-08-22 RU RU2008116598/04A patent/RU2424251C2/en active
- 2006-08-22 AT AT06802002T patent/ATE458011T1/en not_active IP Right Cessation
-
2009
- 2009-01-29 US US12/322,143 patent/US8039562B2/en active Active
Non-Patent Citations (1)
Title |
---|
See references of WO2007037839A1 * |
Also Published As
Publication number | Publication date |
---|---|
WO2007037839A1 (en) | 2007-04-05 |
CN101277983A (en) | 2008-10-01 |
BRPI0616461B1 (en) | 2018-04-24 |
US8039562B2 (en) | 2011-10-18 |
KR20080068029A (en) | 2008-07-22 |
CN105367691A (en) | 2016-03-02 |
DE602006012338D1 (en) | 2010-04-01 |
EP1928921B1 (en) | 2010-02-17 |
JP5069242B2 (en) | 2012-11-07 |
BRPI0616461A2 (en) | 2011-06-21 |
US20090198025A1 (en) | 2009-08-06 |
CA2622258A1 (en) | 2007-04-05 |
RU2008116598A (en) | 2009-11-10 |
ATE458011T1 (en) | 2010-03-15 |
RU2424251C2 (en) | 2011-07-20 |
US20070073012A1 (en) | 2007-03-29 |
JP2009510215A (en) | 2009-03-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8039562B2 (en) | Method for seed bed treatment before a polymerization reaction | |
US5672665A (en) | Process for transitioning between incompatible polymerization catalysts | |
EP0830393B1 (en) | Process for transitioning between incompatible polymerization catalysts | |
US4481301A (en) | Highly active catalyst composition for polymerizing alpha-olefins | |
EP2183286B1 (en) | Continuity additives and their use in polymerization processes | |
US7847036B2 (en) | Method for reducing and/or preventing production of excessively low density polymer product during polymerization transitions | |
US7343225B2 (en) | Method for reducing off-grade product production during reaction transitions | |
JPH04226107A (en) | Catalyst and method for manufacture of epr resin | |
US4988784A (en) | Catalyst for regulating the molecular weight distribution of ethylene polymers | |
CN114656584B (en) | Olefin polymerization process using antistatic agent for metallocene olefin polymerization process | |
EP3044237B1 (en) | Process for the (co-)polymerisation of olefins |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20080331 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE SI SK TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REF | Corresponds to: |
Ref document number: 602006012338 Country of ref document: DE Date of ref document: 20100401 Kind code of ref document: P |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: VDEP Effective date: 20100217 |
|
LTIE | Lt: invalidation of european patent or patent extension |
Effective date: 20100217 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100528 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100217 Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100617 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100617 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100217 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100217 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100217 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100217 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100217 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100217 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100217 Ref country code: BE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100217 Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100217 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100518 Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100217 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100217 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100217 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100517 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100217 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed |
Effective date: 20101118 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100217 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100831 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20100822 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100831 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100831 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100822 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100822 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20100822 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100818 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20100217 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20160822 Year of fee payment: 11 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 12 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: PLFP Year of fee payment: 13 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20170822 |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230525 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20240625 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20240702 Year of fee payment: 19 |